This invention relates to controlled functional density polyamines containing olefinic unsaturation. In one aspect, this invention relates to the production of controlled functional density polyamines having controlled amounts of pendant tertiary amine and pendant secondary amine groups. In another aspect, this invention relates to the production of controlled functional density polyamines having controlled amounts of two different pendant tertiary amine groups. In a further aspect, this invention relates to the production of controlled functional density polyamines containing olefinic unsaturation by selective reaction of carbon-carbon double bonds in the starting polymer containing olefinic unsaturation.
The principle of preparing amines by reacting an olefin with hydrogen, carbon monoxide and a primary or secondary amine is known. Various techniques embodying this principle have been described using various catalysts. Such techniques are generally referred to as aminomethylation reactions.
In J. Org. Chem., 47, 445 (1982), Jachimowicz et al disclose various approaches which have been used in attempts to devise a one-step, efficient and general conversion of olefins to amines. Among the catalysts are iron pentacarbonyl, rhodium oxide, ruthenium/iron carbonyl and iridium catalysts.
U.S. Pat. No. 4,297,481 discloses a process for forming a polymeric polyamine/amide wherein said amino/amide nitrogens are positioned in the polymer backbone by contacting a monomeric nitrogen compound which has at least two labile hydrogens bonded to the nitrogen atoms therein, a monomeric hydrocarbon compound containing at least two olefinic groups therein, carbon monoxide and water in the presence of a catalytic amount of a rhodium-containing compound. This invention describes the use of ammonia or primary amines but does not produce polymers with exclusively pendant secondary amine groups nor does it produce polymers wherein the amount of pendant secondary and tertiary amine groups can be controlled. The preparation of polymers with pendant amine and amide groups is described in U.S. Pat. No. 4,312,965. These polymers are prepared from polymeric polyolefins, carbon monoxide, water and nitrogen compounds such as ammonia and primary or secondary amines. Again, rhodium or a rhodium-containing compound serves as the catalyst. However, this invention describes polymers having a low degree of amine incorporation which predominantly contain tertiary amine groups when primary amines are used as the starting material such that the amount of pendant secondary and tertiary amine groups cannot be controlled.
U.S. Pat. No. 4,503,217 teaches a process for preparing polymeric polyamines from polybutadiene, ammonia and primary or secondary amines, carbon monoxide and hydrogen in the presence of a catalyst system comprising a ruthenium-containing catalyst and a dimethylformamide-alkane mixed solvent which provides a two-phase liquid product, allowing for easy separation of the product polyamine. When primary amines are used in this invention, only the vinyl groups are functionalized, the yield for the amine containing polymers are low, and the resulting polymers are insoluble in organic solvents.
U.S. Pat. No. 4,657,984 discloses preparation of polymeric poly(tertiary amines) from carbon monoxide, hydrogen, polymeric olefins and secondary amines utilizing ruthenium or rhodium phosphines as catalysts. It states that use of these particular catalysts facilitates reaction and hence functionalization of internal as well as vinyl olefin groups.
Thus, the state of the art for preparing polymeric secondary and tertiary polyamines teaches an aminomethylation reaction wherein the vinylic olefins and internal olefins can be reacted utilizing various catalysts under a variety of conditions. However, these reactions are significantly different than the reaction sequence of hydroformylation and reductive amination because there is no teaching in the aminomethylation prior art regarding how to control the degree of functionalization, i.e., the functional density, of either the polyaldehyde or the polyamine prepared therefrom, especially the amounts of different amine pendant groups.
A process which produces controlled functional density polyamines containing residual reactive carbon-carbon double bonds which uses milder reaction conditions, results in higher functional density polymers which contain controlled amounts of pendant tertiary amine and pendant secondary amine groups, or controlled amounts of two different pendant tertiary amine groups, and produces polymers which are soluble in organic solvents would be highly desirable.
The polyamines produced by the process of the present invention are useful in rubber chemicals, such as polymer bound cure accelerators which do not release hazardous volatile materials during curing, polymeric co-activators which cannot migrate from one component to another and polymer bound antioxidants and/or antiozonants with significantly lower tendency to leach out of rubber products, e.g., tires. The polyamines having controlled amounts of pendant tertiary amine groups and pendant secondary amine groups produced by the process of the present invention are also useful in urethane/urea materials, coatings, adhesives, sealants and when the polyamine contains pendant secondary amine groups, construction of three dimensional networks through bonds not available to tertiary amines.